Investigations into the structuring by two-photon polymerization of a nonshrinking, photosensitive, zirconium sol-gel material are presented. This hybrid material can be photostructured even when it contains up to 30 mol % of zirconium propoxide (ZPO); by varying the material's inorganic content, it is possible to modify and tune its refractive index. The introduction of ZPO significantly increases the photosensitivity of the resulting photopolymer. The fabricated three-dimensional photonic crystal structures demonstrate high resolution and a clear band-stop in the near-IR region. In contrast to common practice, no additional effort is required to precompensate for shrinkage or to improve the structural stability of the fabricated photonic crystals; this, combined with the possibility of tuning this material's optical, mechanical, and chemical properties, makes it suitable for a variety of applications by two-photon polymerization manufacturing.

We present a new method for increasing the resolution of direct femtosecond laser writing by multiphoton polymerization, based on quencher diffusion. This method relies on the combination of a mobile quenching molecule with a slow laser scanning speed, allowing the diffusion of the quencher in the scanned area and the depletion of the multiphoton-generated radicals. The material we use is an organic-inorganic hybrid, while the quencher is a photopolymerizable amine-based monomer which is bound on the polymer backbone upon fabrication of the structures. We use this method to fabricate woodpile structures with a 400 nm intralayer period. This is comparable to the results produced by direct laser writing based on stimulated-emission-depletion microscopy, the method considered today as state-of-the-art in 3D structure fabrication. We optically characterize these woodpiles to show that they exhibit well-ordered diffraction patterns and stopgaps down to near-infrared wavelengths. Finally, we model the quencher diffusion, and we show that radical inhibition is responsible for the increased resolution.

The femtosecond laser-induced multi-photon polymerization of a zirconium–silicon based sol–gel photopolymer was employed for the fabrication of a series of micro-optical elements with single and combined optical functions: convex and Fresnel lenses, gratings, solid immersion lenses on a glass slide and on the tip of an optical fiber. The microlenses were produced as polymer caps of varying radii from 10 to 90  µm. The matching of refractive indices between the polymer and substrate was exploited for the creation of composite glass-resist structures which functioned as single lenses. Using this principle, solid immersion lenses were fabricated and their performance demonstrated. The magnification of the composite solid immersion lenses corresponded to the calculated values. The surface roughness of the lenses was below ∼ 30 nm, acceptable for optical applications in the visible range. In addition, the integration of micro-optical elements onto the tip of an optical fiber was demonstrated. To increase the efficiency of the 3D laser polymerization, the lenses were formed by scanning only the outer shell and polymerizing the interior by exposure to UV light.

Laser polymerization has emerged as a direct writing technique allowing the fabrication of complex 3D structures with microscale resolution. The technique provides rapid prototyping capabilities for a broad range of applications, but to meet the growing interest in 3D nanoscale structures the resolution limits need to be pushed beyond the 100 nm benchmark, which is challenging in practical implementations. As a possible path towards this goal, a post processing of laser polymerized structures is presented. Precise control of the cross-sectional dimensions of structural elements as well as tuning of an overall size of the entire 3D structure was achieved by combining isotropic plasma etching and pyrolysis. The smallest obtainable feature sizes are mostly limited by the mechanical properties of the polymerized resist and the geometry of 3D structure. Thus the demonstrated post processing steps open new avenues to explore free form 3D structures at the nanoscale.

The fabrication of fully three-dimensional photonic crystals with a bandgap at optical wavelengths is demonstrated by way of direct femtosecond laser writing of an organic-inorganic hybrid material with metal-binding moieties, and selective silver coating using electroless plating. The crystals have 600-nm intralayer periodicity and sub-100 nm features, and they exhibit well-defined diffraction patterns.

and by exploiting their acute response to their immediate environment, a variety of novel applications have been realized such as negative indices of refraction, [3,4] broadband circular polarization devices, [5] and strongly twisted local electromagnetic fields for sensitive detection of chiral molecules. [6][7][8][9][10] In chiral media, optical activity is a result of the cross-coupling between electric and magnetic fields. Two classical approaches have been proposed to model the mechanisms of optical activity: [11,12] (a) the coupled oscillator model system, where optical activity arises from the coupling of two separate, noncollinear oscillators, and (b) the one-electron model system, where an electron is bound on a helix, giving electric and magnetic character to the optical transitions. Recently, the plasmonic analogue of the coupled oscillator model system, which consists of a system of two cornerstacked gold nanorods, was experimentally demonstrated. [13] This system resembles two coupled, vertically displaced electrons that carry out orthogonal harmonic oscillation driven by an external light field. In this work, we experimentally and theoretically study the plasmonic version of the one-electron model system, which comprises a loop-wire structure, namely the so-called "twisted omega particle." In this case, the 3D plasmonic meta-atom combines a small electric dipole antenna (the metallic wire) and a split-ring resonator (the loop), which exhibits a magnetic dipole resonance leading to a different electromagnetic response to RCP light and the left-handed one (LCP). [14,15] Results and Discussion Fabrication and Optical Characterization Fabrication ApproachTwisted omega architectures have already been theoretically studied and discussed as prototype for plasmonic structures with strong chiro-optical far-field response. [16][17][18][19] To this end, Helgert et al. utilized a layer-by-layer approach to fabricate an architecture reminiscent of the twisted omega by placing two L-shaped gold nanoparticles on top of each other and connected in the vertical direction. [20] Based on a combined spectroscopicThe plasmonic version of a 3D chiral meta-atom which consists of a loopwire structure, namely the so-called twisted omega particle, is experimentally realized. The structure is fabricated by direct laser writing and subsequent electroless silver plating, a novel technique capable of producing truly 3D photonic nanostructures. In this case, the metallic wire of finite length supports an electric dipole resonance, whereas the loop acts as a split-ring resonator which exhibits a magnetic dipole resonance, leading to the separation of right-handed circularly polarized light and the left-handed one. The arising optical activity is discussed in terms of a single oscillator model system used classically to describe the generation of natural optical activity in chiral media, and it is shown that the twisted omega particle acts as its exact plasmonic analogue.

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Two-photon polymerization of photosensitive materials has emerged as a very promising technique for the fabrication of photonic crystals and devices. We present our investigations into the structuring by two-photon polymerization of a new class of photosensitive sol-gel composites exhibiting ultra-low shrinkage. We particularly focus on two composites, the first containing a zirconium alkoxide and the second a nonlinear optical chromophore. The three-dimensional photonic crystal structures fabricated using these materials demonstrate high resolution and clear bandstops in the near IR region.